Triphenylamine-Merocyanine-Based D1-A1-π-A2/A3-D2 Chromophore System: Synthesis, Optoelectronic, and Theoretical Studies

Abstract

donor–acceptorDonor–acceptor–π–acceptor–donor (D1-A1-π-A2/A3-D2)-type small molecules, such TPA-MC-2 and TPA-MC-3, were designed and synthesized starting from donor-substituted alkynes (TPA-MC-1) via [2 + 2] cycloaddition−retroelectrocyclization reaction with tetracyanoethylene (TCNE) and 7,7,8,8-tetracyanoquinodimethane (TCNQ) units, respectively. TPA-MC-2 and TPA-MC-3 chromophores differ on the A2/A3 acceptor subunit, which is 1,1,4,4-tetracyanobutadiene (TCBD) and a dicyanoquinodicyanomethane (DCQDCM), respectively. Both the derivative bearing same donors D1 (triphenylamine) and D2 (trimethylindolinm) and also same A1 (monocyano) as an acceptor, tetracyano with an aryl rings as the π-bridging moiety. The incorporation of TCNE and TCNQ as strong electron withdrawing units led to strong intramolecular charge-transfer (ICT) interactions, resulting in lower LUMO energy levels. Comparative UV–Vis absorption, fluorescence emission, and electrochemical and computational studies were performed to understand the effects of the TCNE and TCNQ subunits incorporated on TPA-MC-2 and TPA-MC-3, respectively.

Keywords

• donor–acceptor
• cyclic voltammograms
• triphenylamine
• tetracyanoethylene
• 7,7,8,8-tetracyanoquinodimethane